Cobalt-Catalyzed Cross-Coupling Reactions of Arylboronic Esters and

New Approaches to the Synthesis of 2,2′: 6′,2″-Terpyridine and Some of Its Derivatives. V. V. Zamalyutin , V. A. Bezdenezhnykh , A. I. Nichugovs...
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Cobalt-Catalyzed Cross-Coupling Reactions of Arylboronic Esters and Aryl Halides Hung A. Duong,* Wenqin Wu, and Yu-Yuan Teo Organic Chemistry, Institute of Chemical and Engineering Sciences (ICES), Agency for Science, Technology and Research (A*STAR), 8 Biomedical Grove, Neuros #07-01, Singapore 138665, Singapore S Supporting Information *

ABSTRACT: An efficient cobalt catalyst system for the Suzuki−Miyaura crosscoupling reaction of arylboronic esters and aryl halides has been identified. In the presence of cobalt(II)/terpyridine catalyst and potassium methoxide, a diverse array of (hetero)biaryls have been prepared in moderate to excellent yields.

T

Scheme 1. Iron- and Cobalt-Catalyzed Suzuki−Miyaura Cross-Coupling Reactions

he Suzuki−Miyaura cross-coupling reaction is currently one of the most frequently employed methods for carbon−carbon bond formation in organic synthesis, including the manufacture of complex small-molecule intermediates and active pharmaceutical ingredients (APIs) on a commercial scale.1 Catalysts based on palladium are predominantly used for this purpose. Palladium, however, is a precious metal with high price volatility and is prohibitively expensive when required in large quantities. Thus, the search for alternative catalytic processes employing inexpensive and highly abundant first-row transition metals such as iron and cobalt represents an important approach toward sustainable chemistry. In comparison to nickel and copper,2,3 much less has been achieved with iron and cobalt as catalyst in the Suzuki−Miyaura reaction, presumably due to the difficulty associated with transmetalation from boron to these earlier transition metals.4 Indeed, iron- and cobalt-catalyzed cross-coupling reactions are generally accomplished with more reactive organometals in Kumada- and Negishi-type reactions.5,6 To facilitate transmetalation, organoboron compounds can be activated by highly reactive organolithium and organomagnesium reagents for cross-coupling reactions under iron catalysis (Scheme 1a).7 Recently, Chirik et al. developed a bis(phosphino)pyridine cobalt catalyst for the cross-coupling of aryl triflates and (benzo)furanylboronic esters in the presence of an alkaline alkoxide (Scheme 1b).8 Presumably, transmetalation was enabled through initial coordination of the oxygen lone pair in the heteroarylboron nucleophile to the metal center. Concurrently, Kumar and Bhat reported an N,N′-bis(phosphino)-2,6-diaminopyridine pincer cobalt acetate complex as catalyst for the cross-coupling of phenylboronic acid and aryl halides (Scheme 1b).9 Notably, the scope of the organoboron nucleophile was not described beyond phenylboronic acid. We report herein a cobalt catalyst system capable of cross-coupling a wide range of organoboronic esters with (hetero)aryl halides, leading to a diverse array of (hetero)biaryl products (Scheme 1b). © XXXX American Chemical Society

To probe any potential reactivity of organoboron compounds under cobalt catalysis, we started out to explore the reactions of different arylboron reagents with 2-chloropyridine (1a), an activated substrate that had been well-studied in ironand cobalt-catalyzed Kumada and Negishi cross-coupling reactions (Table 1).5a,6 After some experimentation with different alkoxides,10 we realized that 3a could be formed in a moderate yield in the reaction of 1a with PhB(neo) (2a) in the presence of 12 mol % of CoCl2 and 1.5 equiv of KOMe (Table 1, entry 1). Since bis(phosphino)pyridine, pyridine diimine, and terpyridine pincer ligands are known to support cobalt complexes in C(sp2)−H borylation and cross-coupling reactions,8,11 we evaluated some easily accessible or commercially available ligands belonging to these families (entries 3− 5). 4′-Phenyl-2,2′:6′,2-terpyridine (TPy) was found to serve as Received: September 26, 2017

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DOI: 10.1021/acs.organomet.7b00726 Organometallics XXXX, XXX, XXX−XXX

Communication

Organometallics Table 1. Optimizations of the Co-Catalyzed Cross-Coupling of 1a and 2a

entry

[Co]

L

solvent

conversn (%)a

yield (%)a

1 2 3 4 5 6 7b 8c 9d 10e 11 12 13 14 15 16f 17g

CoCl2 CoCl2 CoCl2 CoCl2 CoCl2 CoCl2 CoCl2 CoCl2 CoCl2 CoCl2 none PdCl2 NiCl2 CuCl FeCl2 CoCl2 CoCl2

none bipy t BuPNP PDI TPy TPy TPy TPy TPy TPy TPy TPy TPy TPy TPy TPy TPy

THF THF THF THF THF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF

61 87 51 16 100 100 100 47 8 100 16 80 15 9 0 85 52

38 41 31 2 90 94 93 46 7 92 0 12 8 0 0 75 40

Table 2. Scope of Arylboronic Esters in the Co-Catalyzed Reactiona

a

Conditions: 5 mol % of CoCl2, 5 mol % of TPy, 1.5 equiv of ArB(neo), 1.5 equiv of KOMe, DMF, 80 °C, 16 h.

naphthylboronic ester proceeded under cobalt catalysis to give 3f in an excellent yield of 95%. 2-Thienylboronic ester underwent the coupling reaction in 75% yield, whereas the reaction of 2-furanylboronic ester resulted in only 46% of 3h with full consumption of 1a. We suspected that the latter could be due to the instability of the heteroarylboron reagent. However, an increase of 2-furanylboronic ester to 3.0 equiv (in the presence of 1.5 or 3.0 equiv of KOMe) did not help improve the reaction yield. A variety of 2-chloro- and 2-bromopyridines can be coupled with 2a in moderate to excellent yields (Table 3). In comparison to 2-chloropyridine, 2-bromopyridine gave a slightly lower yield in the coupling with 2a to afford 3a in 86% isolated yield. 2-Halopyridines featuring electron-donating and electron-withdrawing groups all gave the arylated products in good yields (3j−l,n). Lower yields were obtained with the highly activated ester 3m, and those featuring a β-substituent (3i,o), presumably due to reduced steric accessibility. Other Nheteroaryl chlorides, including 2-chloroquinoline (3p), 2chloropyrimidine (3q), and 2-chloropyrazine (3r), could be coupled with 2a in good yields. 3-Chloropyridine was less reactive than 3-bromopyridine, affording 3s in only 25% yield as determined by GC analysis. Further exploration reveals that the cobalt-catalyzed reaction is applicable to both π-electron-rich and π-electron-deficient heteroaryl bromides featuring diverse substitution patterns. Heterobiaryls incorporating pyrimidine, imidazole, quinoline, thiophene, and furan units could be prepared in good yields (3u−3aa). Reactions of 2,5-dichloropyridine and 2-chloro-5bromopyridine with a reduced amount of PhB(neo) (1.2 equiv) to minimize diarylation gave the monophenylated products 3ab,ac in 94% and 74% yields, respectively. 2-Chloro-5phenylpyridine was also obtained in 8% yield in the latter. Phenyl (pseudo)halides were poor substrates in the cobaltcatalyzed reaction (Table 4). Chlorobenzene and phenyl tosylate failed to give any trace of 3ad, while the reactions of iodobenzene, bromobenzene, and phenyl triflate resulted in mainly decomposition, presumably due to protodehalogenation.14 Running the reactions at a higher temperature (e.g., 100 °C) did not help improve the reaction yield. This is rather surprising, considering the reactivity displayed by π-electronrich 2-bromothiophene (3z) and 2-bromofuran (3aa) (Table

a

Determined by GC using dodecane as an internal standard. b5 mol % CoCl2 and 5 mol % TP were used, and the reaction was run at 80 °C. c 0.5 equiv of KOMe was employed. dKOtBu was employed instead of KOMe. eKOEt was employed instead of KOMe. fPhB(OH)2 was employed instead of PhB(neo). gPhB(pin) was employed instead of PhB(neo).

an excellent ligand, as 3a was obtained in 90% yield (entry 5). Running the reaction in DMF at 80 °C allowed the catalyst loading to be lowered to 5 mol % without any erosion in yield (entries 6 and 7). A reduction of KOMe to 0.5 equiv led to an incomplete conversion of 1a (entry 8). Regarding the base additive, the activity of KOEt was similar to that of KOMe, whereas sterically hindered tert-butoxide performed poorly in the reaction (entries 9 and 10).12 While the reaction with 99.998% CoCl2 exhibited a comparable level of activity, no product was observed in the absence of a cobalt salt (entry 11). Other metal catalysts (i.e., Pd, Ni, Cu, and Fe) resulted in poor yields of 3a under similar conditions (entries 12−15). These results confirmed cobalt as the active catalyst in this reaction. Reactions employing PhB(OH)2 or PhB(pin) as the organoboron nucleophile were less efficient, resulting in an incomplete conversion of 1a after heating at 80 °C for 16 h (entries 16 and 17).13 The developed conditions were amenable to the crosscoupling of a range of boronic esters with 1a (Table 2). Both electron-rich and electron-deficient arylboronic esters were efficiently coupled with 1a to give 3b,c in 84% and 90% yields, respectively. A moderate yield of 3d was obtained in the reaction of electronically deactivated 4-cyanophenylboronic ester. Sterically hindered 2-methylphenylboronic ester reacted with 1a to give 3e in 78% yield. The reaction of 2B

DOI: 10.1021/acs.organomet.7b00726 Organometallics XXXX, XXX, XXX−XXX

Communication

Organometallics Table 3. Scope of Heteroaryl Halides in the Co-Catalyzed Reactiona

Table 4. Scope of Aryl Halides in the Co-Catalyzed Reactiona

a

Conditions: 5 mol % of CoCl2, 5 mol % of TPy, 1.5 equiv of ArB(neo), 1.5 equiv of KOMe, DMF, 80 °C, 16 h. bDetermined by GC/GCMS analysis.

with 2a to give 3af in 60% yield, whereas less activated 4chlorobenzotrifluoride (3ae) and 4-chloroacetophenone (3ag) resulted in a significant decomposition of the aryl chlorides.14 To probe whether the aryl halide is involved in catalyst activation, we reacted 1af with CoCl2 (1 equiv), TPy (1 equiv), and KOMe (1 equiv) (Scheme 2a). 1af was chosen because the protodebromination product (benzonitrile), if formed, could be monitored by GC/GCMS. However, 1af was fully recovered after the reaction. On the other hand, a stoichiometric reaction Scheme 2. Experiments To Probe Catalyst Activation Pathway a

Conditions: 5 mol % of CoCl2, 5 mol % of TPy, 1.5 equiv of ArB(neo), 1.5 equiv of KOMe, DMF, 80 °C, 16 h. b2-Phenylpyridine (3a) resulting from protodebromination of 3i was also obtained in ca. 14% yield. cDetermined by GC analysis. d1.2 equiv of ArB(neo) and 1.2 equiv of KOMe were used. e2-Chloro-5-phenylpyridine was also obtained in 8% yield.

3). Possibly, initial coordination of the heteroatom in these heterocycles to cobalt promotes the subsequent coupling event. Electron-deficient aryl bromides were coupled with 2a under cobalt catalysis to give 3ae,af in 77% and 74% yields, respectively. 3ag incorporating a ketone functional group could be synthesized in 52% yield. Methyl 3-bromobenzoate was coupled with 2a to give 3ah in 65% yield, whereas 3ai was not formed in the reaction of 1-bromo-3-nitrobenzene, indicating the incompatibility of the cobalt catalyst with a nitro functional group. The reaction of sterically hindered methyl 2-bromobenzoate led to only an 11% yield of 3aj, as determined by GC analysis of the reaction mixture. Both electron-rich and electron-deficient arylboronic esters were effective in the coupling reaction, as 3ak,al were formed in 73% and 93% yields, respectively. 4-Chlorobenzonitrile was coupled C

DOI: 10.1021/acs.organomet.7b00726 Organometallics XXXX, XXX, XXX−XXX

Communication

Organometallics

(3) For a review on copper-catalyzed Suzuki−Miyaura cross-coupling reactions, see: Thapa, S.; Shrestha, B.; Gurung, S. K.; Giri, R. Org. Biomol. Chem. 2015, 13, 4816−4827. (4) (a) Dunsford, J. J.; Clark, E. R.; Ingleson, M. J. Dalton Trans. 2015, 44, 20577−20583. (b) Yu, Y.; Brennessel, W. W.; Holland, P. L. Organometallics 2007, 26, 3217−3226. (5) For some recent examples of iron-catalyzed C(sp2)−C(sp2) cross-coupling, see: (a) Kuzmina, O. M.; Steib, A. K.; Markiewicz, J. T.; Flubacher, D.; Knochel, P. Angew. Chem., Int. Ed. 2013, 52, 4945− 4949. (b) Chua, Y.-Y.; Duong, H. A. Chem. Commun. 2014, 50, 8424− 8427. (c) Agrawal, T.; Cook, S. P. Org. Lett. 2014, 16, 5080−5083. (d) Chua, Y.-Y.; Duong, H. A. Chem. Commun. 2016, 52, 1466−1469. (e) Wu, W.; Teng, Q.; Chua, Y.-Y.; Huynh, H. V.; Duong, H. A. Organometallics 2017, 36, 2293−2297. (6) For reviews on cobalt-catalyzed cross-coupling reactions, see: (a) Gosmini, C.; Bégouin, J.-M.; Moncomble, A. Chem. Commun. 2008, 3221−3233. (b) Cahiez, G.; Moyeux, A. Chem. Rev. 2010, 110, 1435−1462. For examples of reductive coupling of organohalides, see: (c) Amatore, M.; Gosmini, C. Chem. - Eur. J. 2010, 16, 5848−5852. (d) Qian, X.; Auffrant, A.; Felouat, A.; Gosmini, C. Angew. Chem., Int. Ed. 2011, 50, 10402. (e) Cai, Y.; Benischke, A. D.; Knochel, P.; Gosmini, C. Chem. - Eur. J. 2017, 23, 250−253. (7) (a) Hatakeyama, T.; Hashimoto, T.; Kondo, Y.; Fujiwara, Y.; Seike, H.; Takaya, H.; Tamada, Y.; Ono, T.; Nakamura, M. J. Am. Chem. Soc. 2010, 132, 10674−10676. (b) Hashimoto, T.; Hatakeyama, T.; Nakamura, M. J. Org. Chem. 2012, 77, 1168−1173. (c) Hatakeyama, T.; Hashimoto, T.; Kathriarachchi, K. K. A. D. S.; Zenmyo, T.; Seike, H.; Nakamura, M. Angew. Chem., Int. Ed. 2012, 51, 8834−8837. (d) Bedford, R. B.; Brenner, P. B.; Carter, E.; Carvell, T. W.; Cogswell, P. M.; Gallagher, T.; Harvey, J. N.; Murphy, D. M.; Neeve, E. C.; Nunn, J.; Pye, D. R. Chem. - Eur. J. 2014, 20, 7935−7938. (e) Bedford, R. B.; Hall, M. A.; Hodges, G. R.; Huwe, M.; Wilkinson, M. C. Chem. Commun. 2009, 6430−6432. Two retracted papers on iron-catalyzed Suzuki−Miyaura cross-coupling of arylboronic acids and aryl halide: (e2) Kylmälä, T.; Valkonen, A.; Rissanen, K.; Xu, Y.; Franzén, R. Tetrahedron Lett. 2008, 49, 6679−6681. (f) Bézier, D.; Darcel, C. Adv. Synth. Catal. 2009, 351, 1732−1736. (8) Neely, J. M.; Bezdek, M. J.; Chirik, P. J. ACS Cent. Sci. 2016, 2, 935−942. (9) Kumar, L. M.; Bhat, B. R. J. Organomet. Chem. 2017, 827, 41−48. (10) See the Supporting Information for more details on screening of ligands, boron nucleophiles, solvents, and cobalt sources. (11) (a) Obligacion, J. V.; Semproni, S. P.; Chirik, P. J. J. Am. Chem. Soc. 2014, 136, 4133−4136. (b) Léonard, N. G.; Bezdek, M. J.; Chirik, P. J. Organometallics 2017, 36, 142−150. (12) Two different KOMe batches purchased from Fluka and Sigma Aldrich displayed a similar activity. (13) For a comparative study of reactivity difference between arylboron reagents in the Suzuki−Miyaura reaction, see: Zhang, N.; Hoffman, D. J.; Gutsche, N.; Gupta, J.; Percec, V. J. Org. Chem. 2012, 77, 5956−5964 and references therein.. (14) The protodehalogenation products can be observed by GC-MS in several cases, such as in the reactions to prepare 3m,af,ag,ah. (15) Docherty, J. H.; Peng, J.; Dominey, A. P.; Thomas, A. P. Nat. Chem. 2017, 9, 595−600.

of PhB(neo) (2a), CoCl2 (1 equiv), and TPy (1 equiv) (Scheme 2b) proceeded rapidly in the presence of KOMe (entry 1). No conversion was observed in the absence of the base additive (entry 2). These results indicate that catalyst activation likely involves the reduction of Co(II) by an arylborate species. Notably, Thomas et al. reported that an alkoxide such as NaOtBu can form an “ate” species with HBpin or silane that then serves as a reducing agent for cobalt and iron complexes.15 Moreover, a reaction of 0.25 mmol of CoCl2/TPy with excess PhB(neo)/KOMe resulted in only 0.117 mmol of biphenyl even after prolonged heating (Scheme 2b, entry 3). Since the formation of biphenyl from the organoboron is a twoelectron process, a stoichiometry close to 0.5 is in agreement with a reduction of Co(II) to Co(I). Thus, it is possible that Co(II) is reduced by phenylborate to a catalytically active Co(I) species (Scheme 2c) and a Co(I)/Co(III) catalytic cycle similar to that proposed by Chirik et al. could be in operation.8 Further studies are needed to evaluate this hypothesis and to fully elucidate the mechanism of the cobalt-catalyzed reaction. In conclusion, we have developed an efficient cobalt catalyst system for the Suzuki−Miyaura cross-coupling of arylboron reagents and aryl halides. The substrate scope encompasses a broad array of π-electron-rich and π-electron-deficient heteroaryl halides and electron-deficient aryl halides. Further study is now underway to gain more insights into the mechanism of the cobalt-catalyzed reaction and to extend the chemistry to other classes of substrates.

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.7b00726. Experimental details and NMR spectra of the compounds obtained in this paper (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail for H.A.D.: [email protected]. ORCID

Hung A. Duong: 0000-0003-0086-2463 Wenqin Wu: 0000-0002-0081-1458 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The financial support for this work was provided by “GSK-EDB Singapore Partnership for Green and Sustainable Manufacturing” and the Institute of Chemical and Engineering Sciences (ICES), Agency for Science, Technology and Research (A*STAR), Singapore.

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REFERENCES

(1) (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457−2483. (b) Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.; de Meijere, A., Diederich, F.; Eds.; Wiley-VCH: Weinheim, Germany, 2004. (c) Miyaura, N. Cross-Coupling Reactions: A Practical Guide; Springer: Berlin, 2002. (d) Magano, J.; Dunetz, J. R. Chem. Rev. 2011, 111, 2177−2250. (e) Torborg, C.; Beller, M. Adv. Synth. Catal. 2009, 351, 3027−3043. (2) For a review on nickel-catalyzed Suzuki−Miyaura cross-coupling reactions, see: Han, F.-S. Chem. Soc. Rev. 2013, 42, 5270−5298. D

DOI: 10.1021/acs.organomet.7b00726 Organometallics XXXX, XXX, XXX−XXX